US20140106097A1

US20140106097A1 - Process for the production of biodegradable films having improved mechanical properties

Info

Publication number: US20140106097A1
Application number: US14/036,215
Authority: US
Inventors: Catia Bastioli; Gianfranco Del Tredici; Italo Guanella
Original assignee: Novamont SpA
Current assignee: Novamont SpA
Priority date: 2004-06-09
Filing date: 2013-09-25
Publication date: 2014-04-17
Also published as: CA2567323A1; PL1755864T3; EP1755864B1; EP1755864A1; US20070241483A1; ITMI20041150A1; ES2376107T3; WO2005120808A1; AU2005251905A1; NO338782B1; AU2005251905B9; ATE534505T1; EP1755864B2; NO20070126L; PL1755864T5; AU2005251905B2; ES2376107T5

Abstract

Process to produce improved biodegradable plastic films, comprising producing a biodegradable plastic film by bubble blowing, then subjecting it to monoaxial or biaxial cold stretching with a stretch ratio in the range from 1:1 to 1:4.

Description

The present invention relates to a monoaxial or biaxial cold stretching process of a blown film to produce biodegradable films characterized by improved mechanical properties.
The use of biodegradable films to produce products such as bags for separate waste collection, shopping bags, mulch film, diapers, sanitary articles and the like, has grown rapidly in recent years. In particular, products deriving from the processing of biodegradable films obtained from starch and polyester based compositions are currently widely used on the market. The reason for this increased spread of starch based mixtures within the scope of biodegradable plastic materials is linked in particular to the need to use raw materials deriving from renewable sources.
It is important to attempt to reduce the costs of these films in order to allow faster and more widespread penetration of biodegradable materials in the market, also in view of an increased social awareness of problems related to sustainable and eco-compatible development.
An object of the present invention is to provide a process for the production of biodegradable films which makes it possible to obtain products with the appropriate properties related to performance, while at the same time limiting the production costs of said films. The present invention therefore relates to a monoaxial or biaxial cold stretching process for the production of biodegradable films which makes it possible to produce biodegradable films characterized by reduced thickness and superior mechanical properties.
The processes to stretch plastic films (that is, sheets with a thickness which is generally below 200 μm), are known: these are processes to orient films in a longitudinal and/or transverse direction (oriented and bi-oriented films) which allow uniform distribution of the polymer molecules, influencing the mechanical properties of the film in the various directions to increase the stiffness thereof. The prior art also describes stretching processes applied to biodegradable films, in particular deriving from starch based compositions.
EP-0 537 657 describes a stretching process of mono-layer or multi-layer films with at least one layer composed of thermoplastically processable starch, wherein the film is monoaxially or biaxially stretched with a stretch ratio between 1:4 and 1:10, preferably 1:6 and 1:8.5 and even more preferably with a ratio of 1:7 and 1:7.5. The stretching process is performed on an essentially anhydrous film as the initial polymers are dried prior to melting or dehydrated during extrusion. Stretching is performed (see Table 1 of EP-0 537 657) within a temperature range of approximately 90-130° C. At stretch ratios below 1:4 the properties of the film decline significantly. This process generically provides for the possibility of stretching at ambient temperature, although always and only with an anhydrous starch based mixture and with stretch ratios of at least 1:4. The process described there is therefore costly from the viewpoint of energy consumption. Moreover, the stretched films obtained according to said process, although showing an increase in the ultimate tensile strength values, show a considerable increase in the elastic modulus values, making these films particularly stiff, although fragile and with a low tearing strength.
WO 97/22459 discloses a process for producing oriented polyhydroxyalkanoate (PHA) comprising a first stretch at a temperature below 60° C. and a second stretch at a temperature of 60-110° C. The first stretch is carried out before the polymer has fully solidified; the extent of the first stretch is incomplete to permit further stretching.
WO 01/30893 discloses a process for producing polymer products by stretching compositions comprising a biodegradable polyhydroxyalkanoate at a temperature of from (Tg+20° C.) to (Tm−20° C.). Since Tm of the relevant polymer is generally above 100° C., it follows that the stretching process can be carried out also at a temperature above 80° C.
It can be appreciated that the stretch processes described in these two patent documents are carried out at a relatively high temperature, as known in the art. This involves a significant energy consumption.
The drawbacks mentioned above are now surprisingly overcome according to the present invention by subjecting a biodegradable film, after its production by bubble blowing, to a cold stretching process with a stretch ratio greater than 1:1 and less than 1:4, in particular between 1:1.2 and 1:3, and even more particularly between 1:1.5 and 1:2.5, said process making it possible to increase the ultimate tensile strength and yield strength values and to keep the elastic modulus and puncture strength at more or less constant values.
Within the scope of the present invention, cold stretching is intended as stretching performed on the unmelted biodegradable polymer material. More specifically, cold stretching is intended, with reference to films with thickness below 70 μm, as stretching performed at a temperature ranging from 10 to 50° C., preferably between 15 and 40° C. and even more preferably between 20 and 30° C. For films with thickness above 70 μm, the temperatures required for cold stretching may exceed the ranges mentioned above. The process according to the present invention is preferably performed at ambient temperatures but, in relation to the thickness of the films to be subjected to stretching and the composition of the biodegradable polymer material, heating may in fact be necessary to promote the stretching process and make it homogeneous.
The cold stretching process according to the present invention can be implemented on various types of film, for example on single-sheet, single-fold films or directly on tubular films. The cold stretching process according to the present invention can in fact be implemented both discontinuously and in line with the bubble blowing process. If the process is performed in line with the bubble blowing process, this takes place beyond the chill line, that is, subsequent to the height beyond which the bubble has solidified. In this case double bubble blowing processes can also be used.
The biodegradable films obtained with the process according to the present invention are particularly suitable to be used in various fields of application, for example for shopping bags, films for sanitary products and mulching films.
The process according to the present invention is directed to films produced from biodegradable polymer materials. The biodegradable polymer materials that can be used in the process of the present invention may be of various nature, such as, for example, biodegradable aliphatic polyesters, aliphatic-aromatic polyesters, polyhydroxyalkanoates, polyhydroxyacids, polyesteramides. Particularly preferred are biodegradable polymers showing values of the Modulus (measured on blown films with 30 μm thickness) comprised in the range of 40-300 MPa, preferably 60-250 MPa and more preferably 100-200 MPa. In the present description biodegradability means biodegradability according to the EN 13432 standard.
Particularly suitable to be subjected to the process of the invention are films produced from compositions with at least one polysaccharide derivative and at least one biodegradable polymer, in particular a biodegradable aliphatic or aliphatic-aromatic polymer from dicarboxylic acid/diol and/or hydroxy acid. The term polysaccharide comprises in particular starch, cellulose and its derivatives (such as for example cellulose acetate, cellulose proprionate, cellulose acetate propionate, cellulose butyrate), alginates. Polysaccharides can be combined also with proteins.
Particularly preferred are films produced from a composition containing starch and at least one biodegradable aliphatic or aliphatic-aromatic polymer from dicarboxylic acid/diol and/or hydroxy acid.
Examples of diacids are succinic, oxalic, malonic, glutaric, adipic, pimelic, suberic, undecanoic, dodecanoic, azelaic, sebacic and brassylic acid. Particularly preferred are adipic acid, azelaic acid, sebacic acid and brassylic acid or their mixtures.
Specific glycols are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. 1,2- and 1,3-propylene glycol, dipropylene glycol, 1,3-butandiol, 1,4-butandiol, 3-methyl-1,5-pentandiol, 1,6-hexandiol, 1,9-nonandiol, 1,10-decandiol, 1,11-undecandiol, 1,12-dodecandiol, 1,13-tridecandiol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexandimethanol and cyclohexandiol. The compounds can be used alone or in a mixture. Typical hydroxy acids include glycolic acid, lactic acid, 3-hydroxybutyric, 4-hydroxybutyric, 3-hydroxyvaleric, 4-hydroxyvaleric, 6-hydroxycaproic, and also include cyclic esters of hydroxycarboxylic acids, such as glycolide, dimers of glycolic acid, ε-caprolactone and 6-hydroxycaproic acid.
With regard to the aromatic part, the biodegradable polymer used in the films subjected to the process according to the present invention preferably contains a polyfunctional aromatic compound such as a phthalic acid, in particular terephthalic acid, bisphenol A, hydroquinone and the like.
The biodegradable aliphatic or aliphatic-aromatic polymer can advantageously be a thermoplastic copolyester of the saturated-unsaturated type obtained from dicarboxylic acids, diols and unsaturated acids of both natural and synthetic origin
The biodegradable aliphatic or aliphatic-aromatic polymer can be obtained with high molecular weights by adding various organic peroxides in the course of its treatment with peroxide during extrusion.
Particularly preferred are polymers with the aromatic part constituted by terephthalic acid and the aliphatic part constituted by diacid diols and/or hydroxy acids, with branched and straight aliphatic chain C₂-C₂₀(if necessary chain extended with isocyanates, anhydrides or epoxides), and in particular polyesters based on terephthalic acid, adipidic acid or sebacic acid, or azelaic acid and butandiol.
Particularly preferred polymers are polybutylenadipate-co-terephtalate produced by BASF A.G. and marketed with the trademark Ecoflex® and polybutylenadipate-co-terephtalate produced by Eastman under the tradename Eastarbio®.
With reference to the starch component of films to be subjected to the process according to the present invention, the term starch is intended as native starch, preferably corn, potato, tapioca, rice, wheat or pea starch and also starch with high amylose contents and “waxy” starches. Flour, grits, physically and chemically modified starches such as ethoxylated starches, oxypropylated starches, acetate starches, butyrate starches, propionate starches, cationic starches, oxidized starches, reticulated starches, gelatinized starches, destructured starches and starches complexed by polymer structures can also be used. Particularly preferred are destructured starch based films.
Advantageously, the mixture to produce the film may contain one or more plasticizers.
Suitable plasticizers are for example those described in EP-0 575 349, the content of which is intended as incorporated in the present invention. Particularly suitable are glycerol, sorbitol, mannitol, erythritol, polyvinyl alcohol with low molecular weight, as well as the oxyethylated and oxypropylated derivatives of the aforesaid compounds, citrates and acetins. The starting compositions can also contain suitable additives, such as lubricating or dispersing agents, dyes, fillers, etc.
Films suitable to be subjected to the present process can be both mono-layer and multi-layer. In the case of multi-layer films, said films can be constituted by at least one layer of starch based material and by at least one layer of biodegradable polyester as is or mixed with other polyesters.
The cold stretching process according to the present invention makes it possible to produce biodegradable films with reduced thickness and with remarkable mechanical properties. These films are therefore useful to produce products such as all kinds and shapes of bags, in particular bags for separate waste collection, shopping bags, mulch film, diapers, sanitary articles. In particular, it is possible to produce stretched films with thickness in the interval ranging from 5 to 60 μm, preferably from 6 to 40 μm and even more preferably from 8 to 30 μm.
In view of the high yield strength values, the films produced according to the present process are particularly advantageous for the production of shopping bags. Films produced according to the present process can also be advantageously be used as reduced thickness backsheets in diapers, as perforated topsheets in sanitary articles and as films for primary and secondary outer packaging materials.

EXAMPLE 1

A composition constituted by


	Corn starch	29.5%
	Polybutylenadipate-co-terephtalate	64.0%
	(47% terephtalate; 53% adipate; MFI = 2.5 dl/g)
	Glycerol	6.2%
	Erucamide	0.3%

was fed, with the addition of 2.2% of water, to a blown film processing unit obtaining a film with thickness of approximately 31μ. Said film was subsequently subjected to a stretching process at ambient temperature (23° C., 50% relative humidity) and with various stretch ratios, in particular 1:2, 1:3 and 1:4.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows the Stress-Strain curves of said stretched films and of the film as is.

FIG. 2 shows the enlarged detail of the initial part of the curve relative to the stretched film with a ratio of 1:2 which has a characteristic bimodal trend.

FIGS. 3, 4 and 5 instead show the graphs relative to the values of the ultimate tensile strength, the yield strength and modulus tests performed on said films.

Finally, Table 1 shows the values of the mechanical tests relative to the film as such, with thickness of 31 μm and 19 μm, compared to the values of the 31 μm cold stretched film stretched at different temperatures and with stretch ratio of 1:2 until reaching a thickness of 19 μm.
The tests to determine the Tensile Strength, Yield Strength and Modulus were carried out according to the standard ASTM D 882. The puncture strength test was instead carried out on a specimen with a diameter of 7.6 cm positioned on an annular support. The puncture punch with semi-circular head had a Ø=3 mm. The film was tested at 23° C. and 50% of relative humidity with the punch at a speed of 1 m/sec. The film has also been stretched at 15° and 45° C.
The data provided below show that the stretching process according to the present invention makes it possible to obtain a remarkable increase in the mechanical properties with respect to the unstretched biodegradable film.

TABLE 1

	Tensile	Yield	E	Puncture
	Strength σ_b	Strength σ_y	Modulus	Test En_b
Film type	(Mpa)	(Mpa)	(Mpa)	(J/mm)

NFO1U 31 μm	25	11	135	1.81
NFO1U 19 μm	21	9	130	1.72
NFO1U 19 μm from	46	24	140	1.84
stretched 31 μm film
(23° C.)
NFO1U 19 μm from	42	21	138	1.82
stretched 31 μm film
(15° C.)
NFO1U 19 μm from	49	26	143	1.85
stretched 31 μm film
(45° C.)

Claims

1-21. (canceled)

22. A process for producing improved biodegradable plastic films, comprising producing a biodegradable plastic film with thickness below 70 μm by bubble blowing and then subjecting said film to monoaxial or biaxial stretching,

characterized in that said stretching is performed at a temperature ranging from 10 to 50° C. with a stretch ratio in the range from 1:1 to 1:4, and

characterized in that the biodegradable film is produced from one or more biodegradable polymer materials selected from the group consisting of biodegradable aliphatic polyesters, biodegradable aliphatic-aromatic polyesters, biodegradable polyhydroxyalkanoates, biodegradable polyhydroxyacids and biodegradable polyesteramides.

23. The process according to claim 22, characterized by a stretching ratio from 1:1.5 to 1:3.

24. The process according to claim 22, characterized by a stretching ratio from 1:1.5 to 1:2.5.

25. The process according to claim 22, characterized in that the stretching is performed at temperatures ranging from 15 to 40° C.

26. The process according to claim 22, characterized in that the stretching is performed at temperatures between 20 and 30° C.

27. The process according to claim 22, wherein stretching is performed at ambient temperature.

28. The process according to claim 22, characterized in that the biodegradable film is produced from compositions comprising at least one polysaccharide derivative and at least one biodegradable polymer.

29. The process according to claim 22, characterized in that said biodegradable polymer is an aliphatic or aliphatic-aromatic polyester derived from dicarboxylic acid/diol and/or hydroxyl acid.

30. The process according to claim 22, characterized in that said biodegradable film is produced from compositions comprising at least one polysaccharide derivative and at least one biodegradable polymer.

31. The process according to claim 29, characterized in that said film is produced from a composition comprising starch and at least one biodegradable aliphatic or aliphatic-aromatic polyester from dicarboxylic acid/diol and/or hydroxyl acid.

32. The process according to claim 30, characterized in that the aromatic part of the biodegradable polyester comprises terephthalic acid and the aliphatic part comprises a diol/diacid.

33. The process according to claim 31, characterized in that said aliphatic part comprises adipidic acid or sebacic acid or azelaic acid and butandiol.

34. The process according to claim 22, wherein the film subjected to stretching is a single-sheet or a single-fold or a tubular film.

35. The process according to claim 30, wherein said film is a multi-layer film comprising at least one starch based layer and at least one layer of biodegradable polyester as is or mixed with other polyesters.

36. The process according to claim 22, wherein the cold stretching process of the biodegradable film is implemented discontinuously or in line with the bubble blowing process of said film.

37. The process according to claim 36, wherein the stretching process in line with the bubble blowing process takes place beyond the chill line.

38. A stretched film with thickness ranging from 5 to 60 μm, produced according to the cold stretching process described in claim 22.

39. The stretched film according to claim 37, with thickness ranging from 6 to 40 μm.

40. The stretched film according to claim 37, with thickness ranging from 8 to 30 μm.

41. A bag, in particular a bag for separate waste collection, a shopping bag, a mulch film, a diaper, a sanitary article, a film for primary and secondary outer packaging materials, produced from cold stretched biodegradable films according to the process described in claim 22.